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Reactions of Alkenes: Organic Chemistry, 7
Reactions of Alkenes: Organic Chemistry, 7
Reactions of Alkenes: Organic Chemistry, 7
L. G. Wade, Jr.
Chapter 8
Reactions of Alkenes
Chapter 8 2
Electrophilic Addition
• Step 1: Pi electrons attack the electrophile.
Chapter 8 3
Types of Additions
Chapter 8 4
Addition of HX to Alkenes
Chapter 8 5
Mechanism of Addition of HX
Step 1: Protonation of the double bond.
Chapter 8 6
Regioselectivity
• Markovnikov’s Rule: The addition of a proton to
the double bond of an alkene results in a
product with the acidic proton bonded to the
carbon atom that already holds the greater
number of hydrogens.
• Markovnikov’s Rule (extended): In an
electrophilic addition to the alkene, the
electrophile adds in such a way that it
generates the most stable intermediate.
Chapter 8 7
Markovnikov’s Rule
Chapter 8 10
Propagation Steps
• Bromine adds to the double bond forming the
most stable radical possible:
CH3 CH3
Br
tertiary radical (more stable)
Br H Br H
H C C + H Br H C C H + Br
H CH3 H CH3
Chapter 8 11
Anti-Markovnikov Stereochemistry
CH3 CH3
Br
tertiary radical (more stable)
because it is more Br
stable. secondary radical (less stable)
not formed
Chapter 8 12
Hydration of Alkenes
Chapter 8 14
Orientation of Hydration
CH3 H CH3
CH3 C CH CH3 H O H CH3 C CH CH3
+
H
3o, more stable
Rearrangement:
CH3 CH3 CH3
CH3 C CH CH3 CH3 C CH CH3 CH3 C CH CH3
CH3 CH3 OH CH3
Solution
This synthesis requires the addition of HBr to an alkene with Markovnikov orientation. Ionic addition
of HBr gives the correct product.
Chapter 8 17
Solved Problem 2
Convert 1-methylcyclohexanol to 1-bromo-2-methylcyclohexane.
Solution
This synthesis requires the conversion of an alcohol to an alkyl bromide with the bromine atom at the
neighboring carbon atom. This is the anti-Markovnikov product, which could be formed by the radical-
catalyzed addition of HBr to 1-methylcyclohexene.
Chapter 8 18
Solved Problem 2 (Continued)
Solution (Continued)
The two-step synthesis is summarized as follows:
Chapter 8 19
Oxymercuration–Demercuration
Reaction
Chapter 8 22
Mercurinium Ion Opening
• Water adds to the more substituted carbon to
form the Markovnikov product.
• Water approaches the mercurinium ion from
the side opposite the ring (anti addition).
Chapter 8 23
Demercuration Reaction
Chapter 8 26
Solved Problem 3
Show the intermediates and products that result from alkoxymercuration–demercuration of
1-methylcyclopentene, using methanol as the solvent.
Solution
Mercuric acetate adds to 1-methylcyclopentene to give the cyclic mercurinium ion. This ion has a
considerable amount of positive charge on the more substituted tertiary carbon atom. Methanol attacks
this carbon.
Chapter 8 27
Hydroboration of Alkenes
Chapter 8 28
Mechanism of Hydroboration
Chapter 8 29
Stereochemistry of Hydroboration
CH3 CH3
CH3
BH3 THF H H2O2 H
BH2 NaOH
OH
Chapter 8 30
Solved Problem 4
Show how you would convert 1-methylcyclopentanol to 2-methylcyclopentanol.
Solution
Working backward, use hydroboration–oxidation to form 2-methyl cyclopentanol from 1-
methylcyclopentene. The use of (1) and (2) above and below the reaction arrow indicates individual
steps in a two-step sequence.
The 2-methylcyclopentanol that results from this synthesis is the pure trans isomer. This
stereochemical result is discussed in Section 8-7C. 1-Methylcyclopentene is the most substituted
alkene that results from dehydration of 1-methylcyclopentanol. Dehydration of the alcohol would give
the correct alkene.
Chapter 8 31
Solved Problem 5
A norbornene molecule labeled with deuterium is subjected to hydroboration–oxidation. Give the
structures of the intermediates and products.
Solution
The syn addition of BH3 across the double bond of norbornene takes place mostly from the more
accessible outside (exo) face of the double bond. Oxidation gives a product with both the hydrogen
atom and the hydroxyl group in exo positions. (The less accessible inner face of the double bond is
called the endo face.)
Chapter 8 32
Oxidation to Alcohol
Chapter 8 33
Oxidation of a Trialkylborane
Chapter 8 34
Addition of Halogens
Chapter 8 35
Mechanism of Halogen Addition to
Alkenes
meso
Chapter 8 37
Test for Unsaturation
• Add Br2 in CCl4 (dark, red-
brown color) to an alkene.
• The color quickly disappears
as the bromine adds to the
double bond (left-side test
tube).
• If there is no double bond
present the brown color will
remain (right side).
• “Decolorizing bromine” is the
chemical test for the
presence of a double bond.
Chapter 8 38
Formation of Halohydrin
Chapter 8 40
Solved Problem 6
Propose a mechanism for the reaction of 1-methylcyclopentene with bromine water.
Solution
1-Methylcyclopentene reacts with bromine to give a bromonium ion. Attack by water could occur at
either the secondary carbon or the tertiary carbon of the bromonium ion. Attack actually occurs at the
more substituted carbon, which bears more of the positive charge. The product is formed as a racemic
mixture.
Chapter 8 41
Solved Problem 7
When cyclohexene is treated with bromine in saturated aqueous sodium chloride, a mixture of trans-2-
bromocyclohexanol and trans-1-bromo-2-chlorocyclohexane results. Propose a mechanism to account
for these two products.
Solution
Cyclohexene reacts with bromine to give a bromonium ion, which will react with any available
nucleophile. The most abundant nucleophiles in saturated aqueous sodium chloride solution are water
and chloride ions. Attack by water gives the bromohydrin, and attack by chloride gives the dihalide.
Either of these attacks gives anti stereochemistry.
Chapter 8 42
Hydrogenation of Alkenes
Chapter 8 46
Carbenes: Diazomethane
Method
N N CH 2 N N CH 2
diazomethane
H
heat or UV light
N N CH 2 N2 + C
H
carbene
Chapter 8 48
Alpha Elimination Reaction
Chapter 8 49
Stereospecificity
H CH3 H Br CH3
CHBr3
C C
CH3 KOH/H2O CH3 H
H
Br
Chapter 8 50
Carbene Examples
Simmons–Smith Reaction
CH2I2
Zn, CuCl
CHBr3 Br
KOH/H2O Br
Chapter 8 51
Epoxidation
Chapter 8 52
Mechanism
Chapter 8 54
Opening the Epoxide Ring
H
• This process is acid O OH
catalyzed. C C C C
• Water attacks the O
H2O H H
protonated epoxide
on the opposite side
of the ring (back- OH OH
side attack). C C C C
• Anti–diol is formed. O OH
H H2O
H
Chapter 8 55
Syn Hydroxylation of Alkenes
Chapter 8 56
Mechanism with OsO4
Solution
We can reconstruct the alkene by removing the two oxygen atoms of the carbonyl groups (C=O) and
connecting the remaining carbon atoms with a double bond. One uncertainty remains, however: The
original alkene might be either of two possible geometric isomers.
Chapter 8 61
Cleavage with KMnO4
carboxylate
Aldehydes can be
isolated.
Chapter 8 63
Polymerization
Chapter 8 64
Cationic Polymerization
Chapter 8 65
Termination Step of Cationic
Polymerization
Chapter 8 66
Cationic Polymerization Using
BF3 as Catalyst
Chapter 8 67
Radical Polymerization
Chapter 8 69